Disazo dye and method for its preparation



Patented Dec. 26, 1933 ESPATENT O ICE.

DISAZO DYE AND METHOD ronrrs PREPARATION Henry Jordan, Wilmington. Del., assignor to E. I. du Pont de Nemours & Company, Wilmington, DeL, a corporation of Delaware I No Drawing. Application May 17, 1932 SerialNo'. 611,939 j 9 Claims.

This invention relates to dyes and more partic-.-, ularly to azo dyes, especially thoseof the disazo class, and methods for their production.

The object of this invention is to produce a dyestuff having exceptional affinity for natural and regenerated vegetable fiber. A further object is to'produce azo dyes which are exceedingly fast to light and washing. A still further object is to produce dyes which retain their original brilliant shades after repeated washings. Additional objects will appear hereinafter.

These objects are attained. by coupling a diazotized aminoazo compound of the benzene series which contains not more than one sulfo or carboxy groupto an aroyl-amino-aryl-2-amino-5- naphthol-7-sulfonic acid, preferably a benzoylamino-benzoyl-Z-a m i n o--naphthol-7-sulfonic acid.

These new dyes have the following general formula:

in which R1 and R2 are benzene radicals which together contain not more than one sulfo or ca boxy group and R3 and R4 are benzene radicals which preferably should not contain free sulfo, carboxy, amino, or, hydroxylgroups.

This invention may be more completely understood by a consideration of the following examples: I

-Eazample 1 acid solution, maintaining a temperature of C. The diazotization was completed in a few minutes. The diazo compound was then added.

to a solution of 462 parts of benzoyl-para-aminobenzoyl-J-acid in 6000 parts of water and 350 parts of sodium carbonate, maintaining a coupling temperature by the addition of ice of 5-10 C. The 'dye was isolated by heating the coupling to about 90 C. and salting with 10% salt.

The benzoyl-p-amino-benzoyl-J-acid may be prepared by condensing para-'amino-benzoyl-J- acid in aqueous solution with benzoyl chloride at a temperature of 510 C., maintaining a neutral to litmus reaction by theaddition of an equivalent 5 amount of sodium carbonate.

The new dye may also be prepared'by first making the coupling of diazo-aminoazobenzene-sulfonic acid with p-amino-benzoyl-J-acid and then benzoylating the finished dye. The final dye will be identical to the one described above.

1 The new dye was, in its dry ground form; a dark reddish powder, solublein water withia bright bluish-red coloratiomy. in concentrated sulfuric acid with a deep greenish blue coloration. 'It 751 dyed cotton and regenerated cellulose in bright bluish-red shades. The dyeings possessed exceptionally good fastness'to washing, combined withla very good fastnessito light. The new dye most probably had the following formula: r

- since on reduction with stannous chloride the new dye yielded p-sulfanilic acid, para-phenylenediamine and benzoyl-para-amino-benzoyl-Z-amino-5-hydroxy-6-amino naphthalene-7 sulfonic acid. 1 p

I V Example 2 A solution 'of 173 parts of p-sulfanilic acid'in 4000 parts of water and 53 parts of sodium carbonate was iced to 10 C. and acidified with 280 parts of hydrochloric acid (31%). 69 parts of sodium nitrite were thenfadded and the diazotization stirred for 30 -minutes at a temperature of 10-l5 =C. A solution of parts of m-toluidine in 500 parts of water and 132 parts of hydrochloric acid (31%) was then added and the Congo acidity neutralized with 290 parts of sodium acetate. The coupling was allowed to stir 10-12 hours at 20-25 C.- The mixture was then made acid to Congo red with hydrochloric acid and filtered at C. The amino'azobody was then dissolved in 5000 parts of water and 40 parts of sodium hydroxide at 25-30 (3., acidified with 280 parts of hydrochloric acid (31%) and 69 parts of sodium nitrite slowly added, maintaining an excess of nitritefor 1 hours. The mixture was then cooled to 10 C., added to 462 parts of hen zoyl-p-amino-benzoylJ-acid, and finished as in Example 1. The dry powdereddye was dark red in color, dissolving in water it gave a bright bluish-red coloration and in concentrated sulfuric acid it gave a deep greenish-blue shade. It dyed cotton a bright bluish-red shade'of' very good fastness to light and washing. a

l Thedye probably had the following formula:

since on reduction with stannous chloride it yieldedp-sulfanilic acid, Z-methyl-p-phenylenediamine and benzoyl-p-amino-benzoyl-2-amino- 5-hydroxy-6-amino-naphthalene-'l-sulfonic acid.

Example 3" f :;One hundred seventy-three (173) parts of psulfanilic acid was diazotized as. in Example 2 and a solution of 133 .parts of p-Xylidine in 500 parts of water and 132 parts of hydrochloric acid (31%) added. The Congo acidity was neutralized with 290 parts of sodium acetate. After stirring 10-12 hours at 20-25 C. the coupling was completed. The aminoazo body was then filtered off,- diazotized and coupled 'to 462p'arts of benzoylp-amino-benzoyl-J-acidas inExample 2".

The dye was reddish-black in its powdered form; its solution in'water gave a 'bluish-redbol- 7 oration while a deep greenish-blue coloration'w-as' V to light.

produced in concentrated sulfuric acid. It dyed cotton a bluish-red or Bordeaux shade of exceptional fastness to washing and very good fastness The dye probably had the following formula:

since on reduction with stannous chloride it yielded p-sulfanilic acid, 2:5-dimethyl-p-phenylenediamine and benzoyl-p-amino benzoyl 2 amino-S-hydroxy 6 amino-naphthalene '7 sul fonic acid.

Example 4 The diazotized aminoa zo body (p-sulfanilic acid-p-xylidine) prepared as inExample 3 was actly the same manner as in Example 1.

The dye was reddish-black in its powdered form, its solution in water gave a bluish-red coloration while a deep greenish-blue coloration was 'producedin concentrated sulfuric acid. It dyed cotton a bluish-red or Bordeaux shade of good fastness to light and washing. a

The dye probably had the formula:

V 1. l 0113 OH i f X'JH. NaOgS NHCO NHCO since on reduction with stannous chloride it yielded p -sulfanilic acid, 2:5dimethyl-pphenyl- 'enediamine and benzoyl m-amino benz0yl-2- amino-E-hydroxy I 6 amino naphthalene Z sul f onic acid.

been diazotized as in Example 2, 145 parts of was then neutralized with 290 parts of sodium acetate. The coupling was completed after stirring 10-12 hours at 20-25? C." The mixture was then made acid to Congo red paper with hydrochloric acid and filtered at 70? C. The aminoazo compound was then diaaotiz'ed, added to &62 parts of benzoyl-p-amino-benzoyl-J-acid and finished just as in Example 2.

The dry powdered dye was reddish-black in color, dissolving in water it gave a bluish-violet "colorationand 'in concentrated sulfuric acid it i gave a greenish-blue shade.

It dyed cotton a bluish-violet shade of very good fastness to washing. Y

The dye probably had the formula:

since on reduction withstannous chloride it yielded p-sulfanilic" acid, 2-methoxy'-5:-methyl-.p-. ph'enylenediamine and-benzoylp-aminoebenzoyle 2'-amino-5-hydroxy-fi-amino-naphthalenee'l-suL tonic acid; I 1

, I Example 6,

Just. as in Example 2, 173 parts of: oasulfanilic acid were diazotizedand coupled to. m-toluidine and the. resulting aminoazo compound diazotized and coupled to benzoyl-p-aminobenzoyl-J'-acid; The dye, in its my powdered form was a dark reddish color, dissolving only slightlyin hot water and gave a bright bluish-red coloration; In. concentrated sulfuric acid it gave a deep reenish-blue coloration. It dyed cottona bright bluish-red shade of very goodfastness to light and excellent fastness to washing. i

The dye probably had the following formula:

yielded o-sulfanilic acid, :2-methyl-p-phenylenediamine and; benzoyli-p-amino-benzoyl-z-amino- CH3 CH3 7 5-hydroxy-6-amino-naphthalene-7-sulfonic acid.

Example 7 A solution of 187 parts of m -toluidine o-sulfcnic acid in Q0-parts of water and53 parts of sodium carbonatewas iced to 10 C. and acidified with 280; parts ofhydrochloric acid (31%). 69 parts 7 of; sodium, nitrite were then added and the diazo ing.

. The dyeplobably had the following formula:

since {on reduction with stannous chloride it yielded m-toluidine-o-sulfonic acid, Z-methyl-pphenylenediamine and benzoyl-p-amino-benzoyl- 2-amino-5-hydroxy-G-amino-naphthalene-7-sulionic acid.

NaOaS SOaNa Example 8' A solution of 201- parts; of m-xylidine-orsulfonic acid in 4000 parts of water andj53 parts of sodium carbonate was acidified with 280 parts of: hydrochloric acid (31%), and 69 parts of sodium nitrite added. 7 The diazo compound was stirred 30 minutes at 20-25 C. A solution of 133 parts of pxylidine in 500 parts of water and 132 parts of hydrochloric acid (31%) :was added and then 290 parts of sodium acetate to neutralize the Congo acidity. After stirring 10-12 hours at 20-25" C. the resulting aminoazo compound was filtered,

zoyl-J-acid as in'Example 2.

-'The dye was black in its powdered form, its solution in water gave a bluish-red or Bordeaux coloration, while a deep greenish-blue coloration was produced in concentrated sulfuric acid. It

since orrreduction' with stannous chloride. it dyed cotton a bluish-red orB ordeaux. shade. of excellent fastness to washing and light. y The dye probably had the followingformula:

since on reduction with stannous chloride it yielded m-xylidine-o-sulfonic acid, 2:5-dimethylp-phenylenediamine and. benzoyl-p-amino-benzoyl-2-amino-5-hydroxy-6-amino naphthalene- 7-sulfonic acid. l i

- ExampleQ diazotized and. coupled to benzoyl-p-amino-ben- V A solution of 2Q1parts of m xylidine-c-sulfonic acid wasdiazotized as in Example 8. A solution of 245 parts of the sodium salt of m -toluidi ne-.

omega -methane sulfonic acid wasthen added followed .by. 200 parts. of sodium acetate. After stirring 5'hours at 20-25 C. the acidity was cut back with 40 parts of sodium bicarbonate and the stirring continued for 10-15 hours. was then made distinctly acid to Congo red papers with hydrochloric acid and hydrolyzed by heating 1 hours at 80 C.' The aminoazo compound was filtered, diazotized, coupled to benzoylp-aminobenzoyl-J-acid and finished as in Example 2.

The dye was darkred in its dry powdered form,

its solution in water gave a bluish-red coloration, while a deep greenish-blue coloration was produced in concentrated sulfuric acid. It dyed cotton a bluish-red shade of excellent fastness to light and washing.

The dye probably had the following formula:

The mixture amino groups.

since on reduction with stannous chloride it yielded m-xylidine-o-sulfonic acid, Z-methyl-pphenylenediamine and benzoyl-p-amino-benzoyl- 2-amino-5-hydroxy-6 amino-=naphthalene-7-sulfonic acid 7 Example 10 A solution of 137 parts of p-amino-benzoic acid in 4000 parts of. water and 53 parts of sodium carbonate was icedto' 0-59. C; and acidified with 280 parts of hydrochloric acid (31%). 69 parts of sodium nitrite were then added and the diazo stirred for 20-30 minutes at 0-5 C. I A solution of 230 parts of theNa salt of aniline-omegamethane-sulfonic acid was then added, followed by 208 parts ,of sodium acetate. After stirring 8-10 hours the mixture was maderdistinetly acid to Congo red'paper with hydrochloric acid and hydrolyzed by heating 1' hours at C. The

aminoazo compound was then filtered, diazotized,

coupled to benzoyl-p-amino-benzoyl-J-acid and finished as in Example 2. I

The dye was dark red in its dry powdered form, its solution in water gave a bluish-red coloration, while a deep greenish-blue colorationw'as produced in concentrated sulfuric acid. It dyed cotton a bluish-red shade of excellent f astness to light and washin I I I The dye probably had the following formula:

since on reduction with stannous chloride it yielded p-amino-benzoicacid, p-phenylenediamine and benzoyl-p-amino-benzoyl-2-amino-5- hydroxy-G-amino-naphthalene-7=su1fonic acid;

In the above examples very satisfactory results have been obtainedby using in place of theben-' zoyl para amino-benzoyl-J-acid, the corresponding benzoyl -;.m amino benzoyl-J-acid. Very little change was noted when the benzoyle amino-benzoyl-chain had substituted thereon groups such as halogen, alkyl, alkoxy, or nitro. However, it has been found that for optimum results. this benzoyl-amino-benzoyl-chain should not contain free sulfoe, hydroxy, .carboxy or ing.

has the following probable formula:

to. theamino 'group. Meta-amino-benzoic acid in the form of omega-methane-sulfonic acid is one inember of thisgroup which has been used with excellent results. I I The dyes produced by the process of the present invention have exceptional afiinity: for natural and regenerated-vegetable fibers which they dye in beautiful bright shades. The shades produced are exceedingly fast to washing and 'lightand retain their original brilliance and attractiveness after continuedwashing and exposure to..ligh t. This dye= pdssesses a fastness to washing which is greatly superior to any known dye having benzoyl-J-acid as an end component. By the use of a proper reducing discharge medium, the color may be discharged to a pure white thereby permitting very attractive designs to be obtainedby proper-e. ly combiningthe steps of dyeing and discharg As many apparently widely differentembodiments of this invention may be made without departingfrom' the spirit and scope thereof it is understood that I do not limit" myself to the specific embodiments thereof exceptia s defined in the appendedclaims. I 5 'Iclaim: j II w 1. A process for making disazo dyes which comprises coupling a diazotized aminoazo compound ofthe benzene series, containing not more than one sulfo or carbox'y group, toybenzoylamino benzoyle2-ainino-5 naphthol a T- s'ulfdnic acid- 2. A process forr'naking disazo dyes whicca prises coupling a diazo'tizedaminoaz'o compound of the benzene series, containing either a sulfo or V carboxy} group, to benzoyl aminmben'zoyl-zamino-5-naphthol-'7-sulfonic acid.

3. n process for making disazo dyeswhi'ch comprises coupling dia'zotized, p -aminoazobenzene-- p-sulfonic facid to benzoyl-para-amino-benzoyl- 2-aminoe-5-naphthol-7-sulfonic acid.

4. The product substantially identical with that produced by; the process of claim 1,, which I on for example, aniline and the'various toludines, anisidines, xylidines, and cresidines.

. in which R1 and Rs are benzene radicals which together contain not more than one sulfo or carlid boxy group, and R3 and R4 are benzene radicals which do not contain free sulfo, carboxy, amino, or hydroxyl groups.

5. The product substantially identical with that produced by the process of claim 2, which has the following probable formula:

in which R1 and R2 are benzene radicalswhich together contain either a sulfo or a carboxy group, and R3 and R4 are benzene radicals which do not contain free sulfo, carboxy, amino, or hydroxyl groups.

6. The product substantially identical with sisting of methyl and methoxy, diazotizing the resulting aminoazo compound and coupling it with a benzoy1-amino-benzoyl-2-amino-5-naphthol-l-sulfonic acid.

9. An azo dye having the following general formula:

that produced by the process of claim 3, which has the following probable formula:

NaOaS- '7. A secondary disazo dye of the phenylphenyl-naphthyl type having as an end component benzoyl-arnino-benzoyl-Zamino-S-naphthol-7-sulfonic acid, the benzoyl nuclei not containing free sulfo, carboxy, amino, or hydroxyl groups.

8. A process for making disazo dyes which comprises coupling a diazotized member selected wherein Rris a benzene-sulfonic or -carboxylic acid radical which may have substituted thereon methyl and methoxy groups, R2 is a benzene radical which may have substituted thereon methyl and methoxy groups, and R3 and R4 are benzene radicals which do not contain free sulfo, carboxy, amino or hydroxyl groups.

HENRY JORDAN. 

